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US7648742B2 - Difluorosubstituted heterocyclic compounds and the use thereof in the form of components in liquid crystalline media - Google Patents

Difluorosubstituted heterocyclic compounds and the use thereof in the form of components in liquid crystalline media Download PDF

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US7648742B2
US7648742B2 US11/572,759 US57275905A US7648742B2 US 7648742 B2 US7648742 B2 US 7648742B2 US 57275905 A US57275905 A US 57275905A US 7648742 B2 US7648742 B2 US 7648742B2
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Andreas Taugerbeck
Melanie Klasen-Memmer
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/18—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted otherwise than in position 3 or 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K2019/327—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems containing a spiro ring system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
    • C09K2019/3408—Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
    • C09K2019/3425—Six-membered ring with oxygen(s) in fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition

Definitions

  • the present invention relates to difluorosubstituted heterocyclic compounds, a process for their preparation, intermediate compounds for a process for their preparation, their use as components in liquid crystalline media and electrooptical display elements which comprise these liquid crystalline media.
  • the invention relates to difluoro substituted heterocyclic compounds having negative dielectric anisotropy.
  • Liquid crystals have found a wide field of application since the first commercially usable liquid crystalline compounds were found approximately 30 years ago.
  • Known areas of application are, in particular, indicator displays for timepieces and pocket calculators and large display panels, such as are used in railroad stations, airports and sports arenas.
  • Further areas of application are displays of portable computers and navigation systems and also television and video applications. High demands on switching times and the contrast of the images are made, in particular for the last-mentioned applications.
  • the spatial arrangement of the molecules in a liquid crystalline medium causes many of its properties to be direction-dependent. Of importance for use in liquid crystal displays here are, in particular, the anisotropies in the optical, dielectric and electromechanical behavior. Depending on whether the molecules are oriented with their longitudinal axes perpendicular or parallel to the two plates of a capacitor, this has a different capacity; the dielectric constant ⁇ of the liquid crystalline medium is thus of different sizes for the two orientations. Substances whose dielectric constant on perpendicular orientation of the molecular longitudinal axes to the condenser plates is greater than on parallel arrangement are designated as dielectrically positive.
  • the dielectric anisotropy ⁇ ⁇ ⁇ ⁇ ⁇ is greater than zero.
  • both the polarizability of the molecule and permanent dipole moments play a role.
  • the longitudinal axis of the molecules is aligned such that the greater of the dielectric constants is effective.
  • the strength of the interaction with the electric field depends in this case on the difference between the two constants. In the case of small differences, higher switching voltages are necessary than in the case of large ones.
  • suitable polar groups such as, for example, of nitrile groups or fluorine
  • the dipole moment oriented along the molecular longitudinal axis is greater than the dipole moment oriented perpendicularly to the molecular longitudinal axis.
  • the orientation of the greater dipole moment along the longitudinal axis of the molecule also determines the orientation of the molecule in a liquid crystal display in the field-free state.
  • a liquid crystalline layer only approximately 5 to 10 ⁇ m thick is arranged between two plane-parallel glass plates, onto which in each case is evaporated an electrically conductive, transparent layer of tin oxide or indium-tin oxide (ITO) as an electrode.
  • a likewise transparent orientation layer which usually consists of a plastic (e.g. polyimides). It serves to bring the longitudinal axes of the adjacent crystalline molecules into a preferred direction by means of surface forces, such that in the voltage-free state they lie flat on the inside of the display surface uniformly with the same orientation or with the same small tilt angle.
  • a plastic e.g. polyimides
  • two polarization films which only allow linearly polarized light to enter and emerge are applied in a specific arrangement.
  • liquid crystals in which the greater dipole moment is oriented parallel to the longitudinal axis of the molecule, very efficient displays have already been developed.
  • mixtures of 5 to 20 components are usually used in order to achieve an adequately wide temperature range of the mesophase and also short switching times and low threshold voltages.
  • the strong viewing angle dependence however, still causes difficulties in liquid crystal displays such as are used, for example, for laptops.
  • the best image quality can be achieved when the surface of the display is perpendicular to the viewing direction of the observer. If the display is tilted relative to the direction of observation, the image quality is drastically impaired under certain circumstances.
  • An object of the present invention is therefore to make available compounds having advantageous properties for use in liquid crystalline media.
  • they should have a negative dielectric anisotropy which makes them particularly suitable for use in liquid crystalline media for VA displays.
  • the compounds preferably have a negative ⁇ and are therefore particularly suitable for use in VA-TFT displays.
  • the compounds according to the invention have a ⁇ 2 and particularly preferably a ⁇ 5. They show very good compatibility with the customary substances used in liquid crystal mixtures for displays.
  • the compounds of the formula I according to the invention have suitable values of the optical anisotropy ⁇ n, in particular for use in VA-TFT displays.
  • the compounds according to the invention have a ⁇ n of greater than 0.02 and less than 0.40, preferably of greater than 0.04 and less than 0.15.
  • the further physical, physicochemical or electro-optical parameters of the compounds according to the invention are also advantageous for use of the compounds in liquid crystalline media.
  • the compounds in particular have an adequate breadth of the nematic phase and a good low-temperature and long-term stability and also adequately high clear points.
  • the compounds of the formula I according to the invention are furthermore suitable for the preparation of further, optionally more complex mesogenic or liquid crystalline substances which possess a structural element having a benzo-fused and difluoro-substituted oxygen heterocycle.
  • Benzochroman and benzochromene derivatives are preferred here, i.e. e is preferably 1.
  • Benzochroman derivatives of the formula I are particularly preferred, i.e. e is 1 and is a C—C single bond.
  • R 1 and R 2 in formula I in each case independently of one another are an alkanyl radical and/or an alkoxy radical (alkyloxy radical) having 1 to 15 C atoms, these are straight-chain or branched.
  • each of these radicals is straight-chain, has 1, 2, 3, 4, 5, 6 or 7 C atoms and accordingly is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy.
  • R 1 and R 2 in formula I can also independently of one another be thioalkanyl or sulfonalkanyl radicals, i.e. alkanyl radicals in which a CH 2 group is replaced by —S— or —SO 2 —.
  • R 1 and R 2 in formula I can furthermore in each case independently of one another be an alkenyl radical having 2 to 15 C atoms, which is straight-chain or branched and has at least one C—C double bond. Preferably, it is straight-chain and has 2 to 7 C atoms. Accordingly, it is preferably vinyl, prop-1- or prop-2-enyl, but-1-, 2- or but-3-enyl, pent-1-, 2-, 3- or pent-4-enyl, hex-1-, 2-, 3-, 4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, 5- or hept-6-enyl. It the two C atoms of the C—C double bond are substituted, the alkenyl radical can be present as an E and/or Z isomer (trans/cis). In general, the respective E isomers are preferred.
  • At least one of the CH 2 groups in an alkenyl radical can be replaced by oxygen, sulfur or —SO 2 —.
  • an alkenyloxy radical having a terminal oxygen
  • an oxaalkenyl radical having a nonterminal oxygen
  • R 1 and R 2 in formula I can independently of one another also be an alkynyl radical having 2 to 15 C atoms, which is straight-chain or branched and has at least one C—C triple bond.
  • R 1 and R 2 in formula I can in each case independently of one another be an alkanyl radical having 1 to 15 C atoms, in which one CH 2 group is replaced by —O— and one by —CO—, where these are preferably adjacent.
  • This thus comprises an acyloxy group —CO—O— or an oxy-carbonyl group —O—CO—.
  • this radical is straight-chain and has 2 to 6 C atoms.
  • R 1 and R 2 in formula I can in each case independently of one another be an alkenyl radical having 2 to 15 C atoms, in which a CH 2 group, preferably in the neighborhood of an unsubstituted or substituted —C ⁇ C— unit, is replaced by —CO—, —CO—O—, —O—CO— or —O—CO—O—, where this radical can be straight-chain or branched.
  • the radical is straight-chain and has 4 to 13 C atoms.
  • a CH 2 group in an alkynyl radical in particular in the neighborhood of a substituted —C ⁇ C— unit, can also be replaced by —CO—, —CO—O—, —O—CO— or —O—CO—O—.
  • R 1 and R 2 in formula I can in each case independently of one another be an alkanyl radical in which two or more CH 2 groups can be replaced by —O— and/or —CO—O—, where these can be straight-chain or branched. Preferably, it is branched and has 3 to 12 C atoms.
  • R 1 and R 2 in formula I can in each case independently of one another be an alkanyl radical or alkoxy radical having 1 to 15 C atoms, which is monosubstituted by —CN or —CF 3 or a correspondingly substituted alkenyl radical or alkynyl radical having 2 to 15 C atoms, where these are preferably straight-chain.
  • the substitution by —CN or —CF 3 is possible in any desired position.
  • R 1 and R 2 in formula I can in each case independently of one another be an alkanyl radical or alkoxy radical having 1 to 15 C atoms, which is monosubstituted or polysubstituted by F, Cl, Br and/or I, or an alkenyl radical, alkenyloxy radical or alkynyl radical having 2 to 15 C atoms, where these radicals are preferably straight-chain and halogen is preferably —F and/or —Cl. In the case of polysubstitution halogen is preferably —F.
  • the resulting radicals also include perfluorinated radicals such as —CF 3 .
  • the mono- or polyfluorinated radicals are also termed “fluoroalkyl”, “fluoroalkanyl”, “fluoroalkoxy”, “fluoroalkenyl”, “fluoroalkenyloxy” and “fluoroalkynyl”.
  • fluorine or chlorine substituent can be in any desired position, preferably in the ⁇ -position.
  • R 1 and R 2 in formula I can also in each case independently of one another be —F, —Cl, —Br, —I, —CN, —SCN, —NCS OR —SF 5 .
  • R 1 and R 2 in formula I can also independently of one another be a polymerizable or reactive group P; this is distinguished in that it is able to react in a polymerization reaction, e.g. a free radical or ionic chain polymerization, or in a polyaddition or polycondensation, or in that it can be grafted onto a polymer backbone in a manner analogous to a polymerization reaction, for example by condensation or addition.
  • Particularly preferred groups P are those for chain polymerization reactions such as free radical, anionic or cationic polymerization.
  • Very particularly preferred polymerizable groups P are those which comprise a C—C double bond or a C—C triple bond or which can polymerize with ring opening, e.g. oxetanes or epoxides.
  • polymerizable groups P are selected from the group PI, which comprises:
  • a vinyl group, an acrylate group, a methacrylate group, an oxetane group or an epoxy group, especially an acrylate or methacrylate group, may expressly be mentioned.
  • Acrylate and oxetane groups are particularly preferred.
  • the polymerizable group P or P′ can also contain one of the suitable spacers known in the prior art between the actual reactive polymerizable group and the radical or the ring to which the group P or P′ is linked, inter alia ethylene, propylene or butylene.
  • the polymerizable group P is then, for example, a group P′-spacer-, where P′ is one of the abovementioned polymerizable functional radicals P′ and “spacer” is one of the spacers known in the prior art.
  • R 1 and R 2 independently of one another are alkanyl, alkenyl or alkoxy, in each case having up to 8 carbon atoms, hydrogen, fluorine or chlorine, particularly preferably alkanyl, alkoxy, fluorine or hydrogen.
  • R 1 is alkoxy or fluorine and R 2 is alkanyl.
  • Y 1 , Y 2 and Y 3 are preferably independently of one another fluoroalkanyl, fluoroalkenyl, fluoroalkenyloxy or fluoroalkoxy, in each case having up to 4 carbon atoms, hydrogen, fluorine or chlorine.
  • Y 2 and Y 3 are in each case hydrogen and Y 1 is hydrogen, F, C 1 or CF 3 .
  • Y 2 and Y 3 are hydrogen and Y 1 is hydrogen or fluorine, in particular fluorine.
  • the rings A 1 , A 2 , A 3 and 4 are preferably selected independently of one another from the group which comprises
  • Z 1 , Z 2 , Z 3 and Z 4 are independently of one another preferably a single bond, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, —CF 2 CF 2 — or —CH ⁇ CH—, particularly preferably a single bond, —CF 2 O— or —OCF 2 —, in particular a single bond.
  • the one ring is preferably linked to the central heterocycle.
  • two further rings can both be present on the “left” side of the molecule of the formula I or both be present on the “right” side of the molecule of the formula I, or one of the two radicals is linked to the central aromatic ring, while the other is linked to the central O heterocycle.
  • “be linked” means that the respective ring is bonded to the central ring system either directly via a single bond or indirectly via a bridge Z, which is not a single bond.
  • a preferred embodiment of the invention are benzo-chroman derivatives of the formula I, in which a and d are both 0; b is 0 or 1, c is 1; R 1 , if b is 0, is alkanyl or alkoxy, and if b is 1, is F, alkanyl or alkoxy; R 2 is alkanyl or alkoxy; A 2 , if b is 1, is
  • Z 2 if b is 1, is a single bond; and Z 3 is a single bond.
  • R 1 , R 2 , Y 1 , Y 2 and Y 3 have the same meanings and the same preferred meanings as defined above for formula I.
  • R 1 , R 2 , A 2 , A 3 , Z 2 , Z 3 , Y 1 , Y 2 and Y 3 have the same meanings and the same preferred meanings as defined above for formula I.
  • Preferred benzochroman derivatives of the formula I according to the invention, in which a+b+c+d is 2, are shown by the general formulae ID, IE and IF:
  • R 1 , R 2 , A 1 , A 2 , A 3 , Z 1 , Z 2 , Z 3 , Z 4 , Y 1 , Y 2 and Y 3 have the same meanings and the same preferred meanings as defined above for formula I.
  • compounds of the formulae IA to IF are particularly preferred, especially compounds of the formulae IC and IF.
  • Exemplary compounds of the formula IB are the following compounds:
  • n and m independently of one another are 1, 2, 3, 4, 5, 6, 7 or 8, where in the formulae IB-a and IB-c n can also be 0 and in all formulae IB-a to IB-D m can also be 0.
  • Exemplary compounds of the formula IC are the following compounds:
  • n and m independently of one another are 1, 2, 3, 4, 5, 6, 7 or 8, where in the formulae IC-a, IC-b, IC-c and IC-e, n can also be 0 and in all formulae IC-a to IC-f, m can also be 0.
  • Exemplary compounds of the formula IF are the following compounds:
  • n and m independently of one another are 1, 2, 3, 4, 5, 6, 7 or 8, where in the formulae IF-a, IF-c, IF-e, IF-f, IF-h and IF-j, n can also be 0 and in the formulae IF-a, IF-b, IF-e, IF-f, IF-g and IF-j, m can also be 0.
  • the compounds of the general formula I are prepared by methods known per se, as are described in the literature (e.g. in the standard works such as Houben-Weyl, Methoden der organischen Chemie [Methods of organic chemistry], Georg-Thieme-Verlag, Stuttgart), namely under reaction conditions which are known and suitable for the reactions mentioned. Use can be made here of variants which are known per se, but not mentioned here in more detail.
  • the starting substances can optionally also be formed in situ in such a way that they are not isolated from the reaction mixture, but immediately reacted further to give the compounds of the general formula I.
  • the starting substances can be obtained according to generally accessible literature procedures or are commercially available.
  • the fluoride-releasing compound is preferably selected from the group which comprises HF, pyridine-hydrogen fluoride complexes, triethylamine trishydro-fluoride (Et 3 N.3HF) and tetrabutylammonium dihydrogen-trifluoride.
  • pyridine-hydrogen fluoride complexes and triethylamine trishydrofluoride, in particular triethylamine trishydrofluoride are particularly preferred.
  • the oxidant is preferably selected from the group which comprises dimethyldibromohydantoin (DBH), N-chloro-succinimide (NCS), N-bromosuccinimide (NBS), N-iodo-succinimide (NIS), chlorine, bromine, SO 2 Cl 2 , SO 2 ClF, NOBF 4 and chloramine T.
  • DBH dimethyldibromohydantoin
  • NCS N-chloro-succinimide
  • NBS N-bromosuccinimide
  • NIS N-iodo-succinimide
  • chlorine, bromine, SO 2 Cl 2 , SO 2 ClF, NOBF 4 and chloramine T is particularly preferred.
  • reaction conditions of the process according to the invention is not critical per se, provided the reaction of the compound of the formula II to give the compound of the formula I according to the invention proceeds rapidly enough and with adequate selectivity without undesired reaction of reactants, products and reagents.
  • reaction conditions follow from those of analogous oxidative fluorodesulturization reactions for the introduction of —CF 2 O— bridges into open-chain compounds, such as are described, inter alia, in P. Kirsch et al, Angew. Chem. 2001, 113, 1528-1532; WO 01/64667 A1, WO 02/48073 A1 and WO 03/033619 A1.
  • the fluoride-releasing compound is customarily employed in an amount such that—based on the compound of the formula II to be fluorinated approximately 2 to approximately 50 mol equivalents, preferably approximately 5 to approximately 25 mol equivalents and particularly preferably approximately 10 to approximately 20 mol equivalents of fluoride ions are released.
  • this reagent is employed in an amount from approximately 0.65 to approximately 16.7 mol equivalents of the compound, based on the compound of the formula II to be reacted, preferably in an amount from approximately 1.65 to approximately 8.4 mol equivalents and particularly preferably in an amount from approximately 3.3 to approximately 6.6 mol equivalents.
  • the oxidant is customarily used in an amount from approximately 2 to approximately 10 mol equivalents—based on the compound of the formula II to be reacted—, particularly preferably in an amount from approximately 3 to approximately 7 mol equivalents and in particular in an amount from approximately 4.5 to approximately 5.5 mol equivalents.
  • the process according to the invention can be carried out solvent-free and is preferably carried out in a solvent or a mixture of one, two, three or more solvents which is adequately inert to reactants, products and reagents.
  • these are polar solvents or solvent mixtures such as ethers, e.g. diethyl ether, methyl tert-butyl ether and tetra-hydrofuran (THF) and haloalkanes, e.g. dichloro-methane, trichloromethane and trichloroethylene.
  • ethers e.g. diethyl ether, methyl tert-butyl ether and tetra-hydrofuran (THF)
  • haloalkanes e.g. dichloro-methane, trichloromethane and trichloroethylene.
  • an individual solvent is used, in particular dichloromethane.
  • the process according to the invention is carried out in a temperature range from approximately ⁇ 100° C. to approximately 50° C., depending on the reaction rate, selectivity and exothermicity of the reaction.
  • the reaction period is likewise especially determined by the rate at which the reaction according to the invention proceeds, and is customarily between 10 min and 2 days, preferably between 1 hour and 24 hours and in particular between 2 hours and 6 hours.
  • the compounds of the formula II defined above employed in the process according to the invention for the preparation of the compounds of the formula I according to the invention are for their part novel and a further subject of the present invention; here, the radicals, substituents and parameters a, b, c, d, e, R 1 , R 2 , A 1 , A 2 , A 3 , A 4 , Y 1 , Y 2 , Y 3 , Z 1 , Z 2 , Z 3 , Z 4 and assume the same meanings and preferably the same preferred meanings as for formula I.
  • R 3 and R 4 independently of one another are preferably alkanyl radicals having 1, 2, 3, 4, 5 or 6 carbon atoms, in particular methyl, ethyl, n-propyl, i-propyl and n-butyl.
  • R 3 and R 4 can be identical or different and are preferably identical.
  • the bivalent organic radical W 3 having at least two carbon atoms is preferably an alkylene bridge having 2, 3, 4, 5 or 6 carbon atoms in the bridge, where up to three of these carbon atoms in each case can have one or two further C 1 -C 4 -alkanyl substituents; it is also possible that two adjacent carbon atoms of the alkylene bridge for their part are part of a further ring or ring system, such as, for example, in
  • W is preferably a benzene ring which can optionally have further substituents.
  • W 3 is ethylene (—CH 2 —CH 2 —) or propylene (—CH 2 —CH 2 —CH 2 —).
  • the compounds of the formula II according to the invention are for their part accessible in various ways from substances which are known from the literature or commercially obtainable.
  • the compound of the formula II is obtained from a lactone of the general formula III by reaction with a reagent which is obtainable by reaction of approximately 2 mol equivalents of trialkylaluminum with approximately 1 mol equivalent of HS—W 3 —SH and is preferably formed in situ.
  • the lactone has the following formula III
  • the trialkylaluminum employed is a trimethylaluminum.
  • W 3 in the dithiol HS—W 3 —SH has the same meaning and the same preferred meaning as in formula II.
  • the lactone of the formula III can be prepared, for example, as in or analogously to the following scheme 1:
  • the salicylaldehyde A condenses with acetic acid derivatives B to give the lactone C, which can now be employed for its part in the process according to the invention.
  • the endocyclic double bond of C can be reduced under catalytic hydrogenation and the lactone D thus obtained.
  • the salicylaldehyde E is reacted with lithium ester enolates F to give G; by addition of acid, the OH group is eliminated with formation of a C—C double bond, which is subsequently catalytically hydrogenated.
  • the resulting compound H is subsequently converted to the lactone D with acid in methanol or by heating.
  • a further synthesis (scheme 3) is especially suitable for the preparation of lactones of the formula III, in which c and d are both 0 and R 2 is an alkyl radical:
  • the ketone L is converted using the 2-trimethylsilyl-1,3-dithiane M and n-butyllithium and subsequent reaction with tetrabutylammonium fluoride into the ketene dithioketal which for its part is cyclized under acid catalysis to give the spiro compound O, which is a compound of the formula II.
  • the carboxylic acid derivative P is activated using thionyl chloride and then reacted with propane-1,3-dithiol in the presence of trifluoroacetic acid to give the salt Q, which for its part can be reacted with a fluoride-releasing compound and an oxidant to give the desired compound of the formula I.
  • the compounds of the general formula I can be used in liquid crystalline media.
  • the present invention therefore also relates to a liquid crystalline medium having at least two liquid crystalline compounds, comprising at least one compound of the general formula I, where according to the invention the benzochroman derivatives of the formula I with a, b, c, d equal to 0, R 1 , Y 1 and Y 3 equal to hydrogen and Y 2 equal to hydrogen or fluorine and R 2 equal to hydrogen, fluorine or chlorine, which are already known as such in the prior art, can be employed here.
  • the present invention also relates to liquid crystalline media comprising as further constituents, in addition to one or more compounds of the formula I according to the invention, 2 to 40, preferably 4 to 30, components. Particularly preferably, in addition to one or more compounds according to the invention these media contain 7 to 25 components.
  • nematic or nematogenic (monotropic or isotropic) substances are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes consisting of the azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, 1,3-dioxanes, 2,5-tetrahydropyrans, phenyl or cyclohexyl benzoates, cyclohexanecarboxylic acid phenyl or cyclohexyl esters, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters of benzoic acid, of cyclohexanecarboxylic acid, and of cyclohexylcyclohe
  • L and E which can be identical or different, are in each case independently of one another a bivalent radical from the group formed from -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, Thp-, -G-Phe- and -G-Cyc-, and their mirror images, where Phe is 1,4-phenylene unsubstituted or substituted by fluorine, Cyc is trans-1,4-cyclohexylene or 1,4-cyclohexenylene, Pyr is pyrimidine-2,5-diyl or pyridine-2,5-diyl, Dio is 1,3-dioxane-2,5-diyl, Thp is tetrahydropyran-2,5-diyl and G is 2-(trans-1,4
  • one of the radicals L and E is Cyc or Phe.
  • E is preferably Cyc, Phe or Phe-Cyc.
  • the media according to the invention contain one or more components selected from the compounds of the formulae (1), (2), (3), (4) and (5), in which L and E are selected from the group consisting of Cyc and Phe and simultaneously one or more components selected from the compounds of the formulae (1), (2), (3), (4) and (5) in which one of the radicals L and E is selected from the group Cyc and Phe and the other radical is selected from the group -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-, and optionally one or more components selected from the compounds of the formulae (1), (2), (3), (4) and (5) in which the radicals L and E are selected from the group consisting of -Phe-Cyc-, -Cyc-Cyc-, -
  • R′ and R′′ are in each case independently of one another alkyl, alkenyl, alkoxy, alkoxyalkyl(oxaalkyl)alkenyloxy or alkanoyloxy having up to 8 C atoms.
  • group A this smaller subgroup is called group A and the compounds are designated by the subformulae (1a), (2a), (3a), (4a) and (5a).
  • R′ and R′′ are different from one another, where one of these radicals is usually alkyl, alkenyl, alkoxy or alkoxyalkyl(oxaalkyl).
  • R′ and R′′ have the meaning indicated in the case of the compounds of the subformulae (1a) to (5a) and are preferably alkyl, alkenyl, alkoxy or alkoxyalkyl(oxa-alkyl).
  • R′′ is —CN.
  • This subgroup is designated below as group C and the compounds of this subgroup are correspondingly described by subformulae (1c), (2c), (3c), (4c) and (5c)
  • R′ has the meaning indicated in the case of the subformulae (1a) to (5a) and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl(oxa-alkyl).
  • the media according to the invention preferably contain one or more compounds from the groups A, B and/or C.
  • the percentages by weight of the compounds from these groups in the media according to the invention are:
  • the media according to the invention preferably contain 1 to 40%, particularly preferably 5 to 30%, of the compounds of the formula I according to the invention.
  • Media comprising more than 40%, in particular 45 to 90%, of compounds of the formula I according to the invention are furthermore preferred.
  • the media preferably contain one, two, three, four or five compounds of the formula I according to the invention.
  • n independently of one another 1, 2, 3, 4, 5, 6, 7 or 8.
  • the preparation of the media according to the invention is carried out in a manner customary per se.
  • the components are dissolved in one another, preferably at elevated temperature.
  • the liquid crystalline phase of the present invention can be modified such that it can be used in all types of liquid crystal display elements which have hitherto become known.
  • Additives of this type are known to the person skilled in the art and described in detail in the literature (H. Kelker/R. Hatz, Handbook Of Liquid Crystals, Verlag Chemie, Weinheim, 1980).
  • pleochroitic dyes can be added for the preparation of colored guest-host systems or substances can be added for the modification of the dielectric anisotropy, the viscosity and/or the orientation of the nematic phases.
  • the compounds of the formula I are suitable in particular for use in VA-TFT displays.
  • the present invention therefore also relates to electrooptical liquid crystal display elements comprising a liquid crystalline medium according to the invention.
  • ⁇ n is the optical anisotropy (589 nm, 20° C.) and ⁇ is the dielectric anisotropy (1 kHz, 20° C.).
  • halogen is fluorine, chlorine, bromine and iodine.
  • alkyl if not defined differently at another place in this description or in the claims—in its most general meaning is a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon radical having 1 to 15 (i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15) carbon atoms; this radical is unsubstituted or monosubstituted or polysubstituted by fluorine, chlorine, bromine, iodine, carboxyl, nitro, —NH 2 , —N(alkanyl) 2 and/or cyano, where the polysubstitution can take place by the same or by different substituents.
  • the alkyl radical in the aliphatic hydrocarbon chain itself can also be functionalized.
  • alkyl also comprises unsubstituted hydrocarbon radicals or corresponding hydrocarbon radicals which are identically or differently mono- or polysubstituted, in particular by F, Cl, Br, I and/or —CN, in which one or more CH 2 groups can be replaced by —O— (“alkoxyl”, “oxaalkyl”), —S— (“thioalkyl”), —SO 2 —, —CH ⁇ CH—, (“alkenyl”), C ⁇ C— (“alkynyl”), —CO—, —CO—C— or —O—CO— such that heteroatoms (O,S) in the chain are not linked directly to one another.
  • alkyl is a straight-chain or branched unsubstituted or substituted alkanyl, alkenyl or alkoxy radical having 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms.
  • alkyl is an alkanyl radical, this is preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl; CF 3 , CHF 2 , CH 2 F, CF 2 CF 3 .
  • the alkanyl radical is straight-chain and unsubstituted or substituted by F.
  • alkyl also comprises “alkoxy” or “oxaalkyl” radicals.
  • Alkoxy is to be understood as meaning an O-alkyl radical in which the oxygen atom is bonded directly to the group substituted by the alkoxy radical or to the substituted ring and alkyl is defined as above; preferably alkyl is then alkanyl or alkenyl.
  • Preferred alkoxy radicals are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy and octoxy, where each of these radicals can also be substituted, namely preferably by one or more fluorine atoms.
  • alkoxy is —OCH 3 , —OC 2 H 5 , —O-n-C 3 H 7 , —O-n-C 4 H 9 , —O-t-C 4 H 9 , —OCF 3 , —OCHF 2 , —OCHF or —OCHFCHF 2 .
  • oxaalkyl denotes alkyl radicals in which at least one nonterminal CH 2 group is replaced by —O— such that no adjacent heteroatoms (O, S) are present.
  • oxaalkyl comprises straight-chain radicals of the formula C a H 2a+1 —O—(CH 2 ) b —, where a and b in each case independently of one another are 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; particularly preferably, a is an integer from 1 to 6 and b is 1 or 2.
  • thioalkyl comprises a straight-chain radical of the formula C a H 2a+1 —S—(CH 2 ) b —, where a is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 and b is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; particularly preferably, a is an integer from 1 to 6 and b is 0, 1 or 2.
  • the thioalkyl radical can likewise be substituted by F, Cl, Br, I and/or —CN and is preferably unsubstituted.
  • alkenyl is an alkyl radical as defined as above, in which one or more —CH ⁇ CH— groups are present. If two —CH ⁇ CH— groups are present in the radical, this can also be designated as “alkadienyl”.
  • An alkenyl radical can contain 2 to 15 (i.e. 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15) carbon atoms and is branched-chain or preferably straight-chain.
  • the radical is unsubstituted or mono- or polysubstituted identically or differently, in particular by F, Cl, Br, I and/or —CN, i.e.
  • one or both hydrogens of the —CH ⁇ CH— unit and/or one or more hydrogens of the further CH 2 or CH 3 groups of the alkenyl radical can be replaced by the corresponding substituent(s).
  • one or more CH 2 groups can in each case independently of one another be substituted by —O—, —S—, —C ⁇ C—, —CO—, —CO—O— or —O—CO— such that heteroatoms (O, S) are not linked directly to one another.
  • Alkenyl radicals in which one CH 2 group is replaced by —O— is also designated here as “alkenyloxy”.
  • the CH ⁇ CH group carries a radical other than hydrogen on both carbon atoms, for example if it is a nonterminal group, the CH ⁇ CH group can be present in two configurations, namely as the E isomer and as the Z isomer. The same applies for the double bond groups substituted by halogen and/or —CN. In general, the E isomer (trans) is preferred.
  • the alkenyl radical contains 2, 3, 4, 5, 6 or 7 carbon atoms and is vinyl, allyl, 1E-propenyl, 2-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 2-propenyl, 2E-butenyl, 2E-pentenyl, 2E-hexenyl, 2E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl and 6-heptenyl, Particularly preferred alkenyl radicals are vinyl, allyl, 1E-propenyl, 2-propenyl and 3E-butenyl.
  • an alkynyl radical is present.
  • the replacement of one or more CH 2 groups by —CO—O— or —O—CO— is also possible.
  • the following of these radicals are preferred here: acetyloxy, propionyloxy, butyryl-oxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxy-methyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-acetyloxypropyl, 3-propionyloxy-propyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxy-carbonyl, propoxycarbonyl, butoxycarbonyl, pentoxy-carbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl,
  • this radical can be straight-chain or branched. Preferably, it is straight-chain and has 4 to 12 C atoms.
  • acryloyloxymethyl 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, methacryloyloxymethyl, 2-methacryloyloxyethyl, 3-methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl or 8-methacryloyloxyoctyl.
  • alkyl radical, alkanyl radical, alkenyl radical or alkoxy radical is substituted by at least one halogen
  • this radical is preferably straight-chain.
  • Halogen is preferably F or Cl.
  • halogen is preferably F.
  • the resulting radicals also include perfluorinated radicals.
  • the fluorine or chlorine substituent can be in any desired position, but preferably in the ⁇ position.
  • fluoroalkyl designates an alkyl radical as defined above, which is substituted by one or more fluorine atoms.
  • the fluoroalkyl radical has 1 to 7 carbon atoms.
  • Particularly preferred fluoro alkyl radicals are, in addition to CF 3 and CHF 2 , highly fluorinated alkyl radicals such as C 2 F 5 , CHFCF 3 and CHFCHF 2 .
  • fluoroalkoxyl designates an alkoxy radical as defined above, which is substituted by one or more fluorine atoms.
  • the fluoroalkoxy radical has 1 to 7 carbon atoms.
  • Particularly preferred fluoro-alkoxy radicals are, in addition to OCF 3 , OCHF 2 and OCH 2 F, highly fluorinated alkoxy radicals such as OC 2 F 5 , OCHFCF 3 and OCHFCHF 2 .
  • aryl if it is not defined differently in the individual cases in another position in the description or in the claims—means an aromatic hydrocarbon having 6 to 14 carbon atoms, which is optionally mono- or polysubstituted by halogen, nitro, alkanyl, alkoxy, —NH 2 or by —N(alkanyl) 2 , where the polysubstitution can take place with the same or with different substituents.
  • the expression also comprises aromatic hydrocarbons having more than one ring, i.e. fused ring systems and ring systems having rings linked via single or double bonds.
  • “aryl” is an unsubstituted or substituted phenyl, naphthyl or 4,4′-biphenyl radical.
  • aralkyl represents an arylalkyl radical, i.e. a radical in which an aryl substituent is linked to an atom, a chain, another radical or a functional group via an alkyl bridge.
  • the alkyl bridge is preferably a saturated bivalent hydrocarbon radical (“alkylene”), in particular methylene (—CH 2 —) and ethylene (—CH 2 —CH 2 —).
  • alkylene saturated bivalent hydrocarbon radical
  • Preferred examples of an aralkyl radical are benzyl and phenethyl.
  • an “aralkyl-O— radical” is an aralkyl radical which is linked to a further atom, a chain, another radical or a functional group via an oxygen atom bonded to the alkyl bridge.
  • Preferred examples of an aralkyl-O— radical are O-benzyl and O—CH 2 CH 2 phenyl.
  • alkylenel or “alkylene bridge”—if the terms are not defined differently in another position in this description or in the claims—represents a bivalent aliphatic hydrocarbon radical having 1, 2, 3, 4, 5, 6, 7, 8 carbon atoms in the chain, which can optionally also be mono- or polysubstituted by halogen, CN, carboxyl, nitro, alkanyl, alkoxy, —NH 2 or by —N(alkanyl) 2 , where the polysubstitution can take place by the same or by different substituents.
  • alkylene or “alkylene bridge” represents a straight-chain, saturated aliphatic radical having 1, 2, 3, 4, 5, 6 carbon atoms, which is unsubstituted or mono- or disubstituted by methyl, in particular —CH 2 —CH 2 —, —CH 2 —CH 2 —CH 2 —, —(CH 2 ) 4 — and —CH 2 C(CH 3 ) 2 CH 2 —.
  • radicals or substituents of the compounds according to the invention or the compounds according to the invention themselves are present as optically active or stereoisomeric radicals, substituents or compounds because they have, for example, an asymmetric center, these are additionally comprised by the present invention.
  • the compounds of the general formula I according to the invention can be present in isomerically pure form, for example as pure enantiomers, diastereomers, E or Z isomers, trans or cis isomers, or as a mixture of a number of isomers in any desired ratio, for example as a racemate, E/Z isomer mixture or as a cis/trans isomer mixture.
  • protective groups can be employed which are removed again after reaction has taken place.
  • Methods for the use of suitable protective groups are known to the person skilled in the art and described, for example, in T. W. Green, P. G. M. Wuts: Protective Groups in Organic Synthesis, 3rd Ed., John Wiley & Sons (1999).
  • the starting substances can be obtained according to generally accessible literature procedures or commercially.
  • the reactions described are known from the literature.
  • the following abbreviations are used:
  • the dielectric anisotropy ⁇ is determined at 20° C. and 1 kHz.
  • the optical anisotropy ⁇ n is determined at 20° C. and a wavelength of 589.3 nm.
  • 29 ml (58 mmol) of a 2 M solution of trimethylaluminum in heptane are initially introduced into 50 ml of dichloromethane under nitrogen, cooled to ⁇ 75° C., and a solution of 2.9 ml (28.9 mmol) of 1,3-propanedithiol in 15 ml of dichloromethane is added dropwise.
  • the mixture is allowed to thaw and is cooled to ⁇ 20° C., and a solution of 6.80 g (27.6 mmol) of 3-heptyl-3,4-dihydrochromen-2-one (6) in 35 ml of dichloromethane is added dropwise.
  • Example A b In analogy to the synthesis described above in Example A b), starting from 10.1 g of 7-butoxy-8-fluoro-3-[4-(4-trans-pentylcyclohexyl)phenyl]chroman-2-one (14), 8.7 g (70%) of 9-fluoro-10-butoxy-15-(4-trans-pentyl-(4-cyclohexylphenyl))-7-oxa-1,5-dithia[8,13]benzospiro-[5.5]undecane (15) are obtained as a colorless solid.
  • Example A b In analogy to the synthesis described in Example A b), starting from 9.10 g (26.9 mmol) of 7-ethoxy-8-fluoro-3-(4-trans-propylcyclohexyl)chroman-2-one (23), 5.60 g (49%) of 10-ethoxy-9-fluoro-15-(4-trans-propylcyclo-hexyl)-7-oxa-1,5-dithia[8,13]benzospiro[5.5]undecane (24) are obtained as a colorless solid.
  • dithioorthoester 27 5.00 g (22.3 mmol) of dithioorthoester 27 are dissolved in 120 ml of dichloromethane and first treated with 18 ml (0.111 mol) of triethylamine trishydrofluoride at ⁇ 75° C. Subsequently, a suspension of 31.9 g (0.111 mol) of 1,3-dibromo-5,5-dimethylhydantoin are added in portions in 50 ml of dichloromethane in the course of 30 min. The mixture is stirred for a further 2.5 h, warmed to room temperature, hydrolyzed using 1 N sodium hydroxide solution and extracted three times with dichloromethane.
  • Example No. R 1 R 2 953, 1058, 1163, 1268, 1373 H CH 3 954, 1059, 1164, 1269, 1374 H C 2 H 5 955, 1060, 1165, 1270, 1375 H n-C 3 H 7 956, 1061, 1166, 1271, 1376 H n-C 4 H 9 957, 1062, 1167, 1272, 1377 H n-C 5 H 11 958, 1063, 1168, 1273, 1378 H n-C 6 H 13 959, 1064, 1169, 1274, 1379 H n-C 7 H 15 960, 1065, 1170, 1275, 1380 CH 3 CH 3 961, 1066, 1171, 1276, 1381 CH 3 C 2 H 5 962, 1067, 1172, 1277, 1382 CH 3 n-C 3 H 7 963, 1068, 1173, 1278, 1383 CH 3 n-C 4 H 9 964, 1069, 1174, 1279, 1384 CH 3 n-C
  • Example No. R 1 R 2 1534, 1590, H CH 3 1535, 1591, H C 2 H 5 1536, 1592, H n-C 3 H 7 1537, 1593, H n-C 4 H 9 1538, 1594, H n-C 5 H 11 1539, 1595, H n-C 6 H 13 1540, 1596, H n-C 7 H 15 1541, 1597, CH 3 CH 3 1542, 1598, CH 3 C 2 H 5 1543, 1599, CH 3 n-C 3 H 7 1544, 1600, CH 3 n-C 4 H 9 1545, 1601, CH 3 n-C 5 H 11 1546, 1602, CH 3 n-C 6 H 13 1547, 1603, CH 3 n-C 7 H 15 1548, 1604, C 2 H 5 CH 3 1549, 1605, C 2 H 5 C 2 H 5 1550, 1606, C 2 H 5 n-C 3 H 7 1551, 1607, C 2 H 5 n-C 4 H 9 1552, 1608, C

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US20080071097A1 (en) 2008-03-20
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